Azo compounds from alkyl alpha-anilino toluates

ABSTRACT

MONOAZO COMPOUNDS OF THE FORMULA   ((R3-PHENYL)-R2-N(-R&#39;&#39;-N=N-R)-CH2-),(R4-OOC-)BENZENE   WHEREIN R IS 2-THIAZOLYL, 2-BENZOTHIAZOLYL, 2-THIADIAZOLYL OR 2-THIENYL; R&#39;&#39; IS P-PHENYLENE OR 1,4-NAPHTHALENE; R2 IS ALKYLENE OF 1 TO 2 CARBON ATOMS; R3 IS HYDROGEN, LOWER ALKYL, LOWER ALKOXY, HALOGEN, HYDROXY OR LOWER ALKOXYCARBONYL; R4 IS LOWER ALKYL WHICH DYES ARE USEFUL FOR DYEING POLYESTER FIBERS IN YELLOW TO BLUE SHADES WITH IMPROVED BUILD UP, EXCELLENT BRIGHTNESS, SUPERIOR LIGHT FASTNESS, AND SUPERIOR RESISTANCE TO SUBLIMATION.

' Patent 3,816,388 Patented June 11, 1974 3,816,388 AZO COMPOUNDS FROMALKYL ALPHA- ANILINO TOLUATES Max A. Weaver, Herman S. Pridgen, andClarence A. Coates, Jr., Kingsport, Tenn., assignors to Eastman KodakCompany, Rochester, N.Y.

No Drawing. Original application Nov. 5, 1968, Ser. No. 773,656, nowPatent No. 3,660,374. Divided and this application Jan. 28, 1972, Ser.No. 221,761

Int. Cl. C09b 29/08, 29/24; D06p 3/52 US. Cl. 260-152 11 Claims ABSTRACTOF THE DISCLOSURE Monoazo compounds of the formula wherein R isZ-thiazolyl, 2-benzothiazolyl, Z-thiadiazolyl or Z-thienyl; R isp-phenylene or 1,4-napthalene; R is alkylene of 1 or 2 carbon atoms; R,is hydrogen, lower alkyl, lower alkoxy, halogen, hydroxy or loweralkoxycarbonyl; R is lower alkyl which dyes are useful for dyeingpolyester fibers in yellow to blue shades with improved build up,excellent brightness, superior light fastness, and superior resistanceto sublimation.

This application is a divisional application of our Application Ser. No.773,656, filed Nov. 5, 1968, for Azo Compounds from Alkyla-Anilinotoluates, now US. Pat. 3,660,374.

This invention relates to certain monoazo compounds and to polyestertextile materials dyed with the novel monoazo compounds.

The novel monoazo compounds of the invention have the general formulawherein When applied to polyester textile materials according toconventional dyeing procedures, the compounds of the invention exhibitimproved build-up, excellent brightness, and superior fastnessproperties, such as fastness to light and resistance to sublimation. Thenovel azo compounds impart various shades, ranging from yellow to blue,to polyester fibers. The improved fastness properties possessed by thenovel azo compounds allows them to be employed in the dyeing ofcotton-polyester fabrics receiving durable press processing. Thesuperior sublimation fastness possessed by the compounds of theinvention renders them particularly useful in the thermal fixationtechnique of dyeing polyester materials.

The diazo component represented by R can be unsubstituted, or,preferably, substituted with, for example, lower alkyl, lower alkoxy,aryl, nitro, halogen, lower alkylthio, lower alkoxycarbonylalkylthio,cyclohexylthio, arylthio, lower aralkylthio, formyl, lower alkanoyl,lower alkoxycarbonyl, aroyl, lower alkanoylamino, aroylamino, cyano,lower alkylsulfonyl, arylsulfonyl, lower alkylsulfonamido,trifiuoromethyl, sulfamoyl, lower alkylsulfamoyl, carbamoyl, loweralkylcarbamoyl, thiocyanato, etc. The alkanoyl groups can be substitutedwith substituents such as halogen, phenyl, cyano, lower alkoxy, loweralkylthio, lower alkylsulfonyl, etc. The alkylsulfonyl groups can alsobe substituted, for example, with cyano, hydroxy, halogen and the like.The alkoxycarbonyl groups can be substituted, for example, with hydroxyor cyano. As used herein to describe a group containing an alkyl moiety,lower designates a carbon content from 1 to about 4 carbon atoms.Examples of the alkyl and alkoxy groups which can be present on thediazo components include methyl, ethyl, isopropyl, propyl, butyl,methoxy, ethoxy, propoxy, butoxy, etc. Chlorine and bromine are typicalhalogen atoms. Methylsulfonyl, ethylsulfonyl, propylsulfonyl, 2cyanoethylsulfonyl, 2 hydroxyethylsulfonyl, acetyl, propionyl, butyryl,isobutyryl, 3-chloropropionyl, cyanoacetyl, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, 2 cyanoethoxycarbonyl, 2hydroxyethoxycarbonyl, etc. are examples of the alkylsulfonyl, alkanoyl,and alkoxycarbonyl groups which can be present on the groups representedby R.

Acetamido, propionamido, methylsulfonamido, ethylsulfonamido, andbutylsulfonamido are tyupical alkanoylamino and alkylsulfonamidosubstituents which can be present on the diazo component.Dimethylsulfamoyl, ethylsulfamoyl, butylsulfamoyl, diethylcarbamoyl,propylcarbamoyl, dibutylcarbamoyl are examples of the alkylsulfamoyl andalkylcarbamoyl groups. The aryl groups which can be present on the diazocomponent including the aryl moiety of the arylthio, aralkylthio, aroyland arylsulfonyl groups are preferably monocyclic, carbocyclic aryl suchas phenyl and phenyl substituted, for example, with lower alkyl, e.g.tolyl; lower alkoxy, e.g. anisyl; halogen, e.g. chlorophenyl,bromophenyl; etc. Benzoyl, p-toloyl, p-chlorobenzoyl, p-nitrobenzoyl,p-ethoxyphenylthio, p-chlorobenzylthio, benzamido, p-toluoylamino,p-tolylsulfonyl, pethoxyphenylsulfonyl, etc. are examples of thearyl-containing groups which can be present on the groups represented byR. The acyl groups set forth below in the definition of A are furtherexamples of the groups which can be present on the diazo component.

Illustrative of the phenyl groups which R can represent are2-chloro-4-nitrophenyl, 4-nitrophenyl, 2-chloro-4-methylsulfonyl,2,4-di(methylsnlfonyl)phenyl, 2-methylsulfonyl-4-nitrophenyl,2-nitro-4-methylsulfonylphcnyl, 2-acetyl-4-nitrophenyl,2-ethoxycarbonyl-4-nitrophenyl, 2,4-dinitro-6-chlorophenyl,Z-cyano-4,6-dinitrophenyl, 4-methoxycarbonylphenyl,2-ethylsultonyl-4,6-dinitrophenyl, 2-tormyl-4,6-dinitrophenyl,2,4-dinitro-6-propionylphenyl, 2-ethoxycarbonyl-4,G-dinitrophenyl,2-trifluoromethyl-4-nitr0phenyl,

3 2,4-dicyanophenyl, 2-bromo-6-cyano-4-nitrophenyl,4-nitro-2-sulfarnoylphenyl, 2-nitro-4- (dimethyl)sulfamoylphenyl,4-cyanophenyl, 4-methylsulfonylphenyl, 4-trifluoromethylphenyl,4-chlorophenyl, 4-ethylsulfamoylphenyl, 4-acetylphenyl,4-ethylcarbamoylphenyl, Z-carbamoyl-4-nitrophenyl,2-methylsulfonyl-4-thiocyanatophenyl, 2,6-dichloro-4-nitrophenyl,2-nitro-4-thiocyanatophenyl, 2-chloro-6-cyano-4-nitrophenyl,2-cyano-4-nitrophenyl, 2-chloro-4-cyanopheny1,2-chloro-4-ethoxy-carbonylphenyl, and the like.

Preferably, the substituted phenyl group R contains not more than threesubstituents at the para and ortho position.

Typical heterocyclic groups represented by R include 2-thiazolyl,

5-nitro-2-thiazolyl, 5-bromo-2-thiazolyl, S-thiocyanato-Z-thiazolyl,4-trifluoromethyl-Z-thiazolyl, 4-ethoxycarbonyl-Z-thiazolyl,S-cyano-Z-thiazolyl, 5-acetamido-2-thiazolyl,4-methylsulfonyl-2-thiazolyl, 4-methyl-5-nitro-2-thiazolyl,Z-benzothiazolyl, 6-methylsulfonyl-2-benzothiazolyl,6-ethoxycarbonyl-2-benzothiazolyl, 6-cyano-2-benzothiazolyl,6-sulfamoyl-Z-benzothiazolyl, 6-thiocyanato-2-benzothiazolyl,6-N,N-di-methylsulfamoyl-Z-benzothiaz0lyl,4,6-dichloro-2-benzothiazolyl, 4-methyl-6-nitro-2-benzothiazolyl,S-methyl-l,3,4-thiadiazol-2-yl, S-thiocyanato-l,3,4-thiadiazol-2-yl,5-cyclohexylthio-1,3,4-thiadiazol-2-yl,S-ethylthio-1,3,4-thiadiazol-2-yl, 5-phenylthio-1,3,4-thiadiazol-2-yl,S-acetamido-1,3,4-thiadiazol-2-yl, 5-chloro-1,3,4-thiadiazol-2yl,S-beta-cyanoethylthio-1,3,4-thiadiazo1-2-yl,5-ethoxycarbonylmethylthio-1,3,4-thiadiazol-2-yl,S-phenylsulfonyl-1,3,4-thiadiazol-2-yl,3-methylsulfonyl-1,2,4-thiadiazol-5-yl,3-butylthio-1,2,4-thiadiazol-5-yl, 5-benzoy1-3-nitro-2-thienyl,3-nitro-5-p-toluoyl-2-thienyl, 3,5-di-(methylsulfonyl -2-thienyl,

5 -methylsulfonyl-3-nitro-2-thienyl, 5-ethylsulfamoyl-3-nitro-2-thienyl,S-ethoxycarbonyl-Z-thienyl, 3,5-dinitro-2-thienyl,

3-nitro-2-thienyl, etc.

Preferred groups represented by -R have the formula RQ' REi- R 1 u orwherein R is hydrogen, halogen, cyano or nitro;

R is nitro, lower alkylsulfonyl, thiocyanato or sulfamoyl;

R is hydrogen, halogen, formyl; lower alkanoyl, lower alkoxycarbonyl,trifluoromethyl, lower alkylsulfonyl, cyano, sulfamoyl, or carbamoyl;

R is lower alkyl, lower alkoxy, nitro, halogen, lower alkylsulfonyl,carbamoyl, lower alkylcarbamoyl, lower alkoxycarbonyl, sulfamoyl, loweralkylsulfamoyl, cyano, thiocyanato, trifluoromethyl, phenyl orsubstituted phenyl;

R is lower alkyl, lower alkoxy, nitro, halogen, lower alkylsulfonyl,substituted lower alkylsulfonyl, carbamoyl, lower alkylcarbamoyl, loweralkoxycarbonyl, sulfamoyl, lower alkyl sulfamoyl, cyano, thiocyanato,lower alkylthio, cyclohexylthio, phenylthio, substituted phenylthio, ortrifiuorornethyl;

R is lower alkyl, lower alkoxy, halogen, lower alkylthio, benzylthio,cyclohexylthio, phenylthio, substituted phenylthio, phenyl, substitutedphenyl, benzyl, lower alkylsulfonyl, lower alkanoylamino, loweralkylsulfonamido, benzarnido, lower alkoxycarbonyl, loweralkoxycarbonylalkylthio, thiocyanato, sulfamoyl, or loweralkylsulfarnoyl;

R is lower alkylthio, cyclohexylthio, benzylthio, or loweralkylsulfonyl; and

R is lower alkanoyl, benzoyl, or substituted benzoyl.

Examples of the alkyl and alkoxy groups and halogen atoms which can bepresent on the phenylene and naphthylene groups represented by R are setforth above in the definition of the diazo groups. The acyl groupsrepresented by A in the group-NHA, which can be present on the phenylenering represented by R, can be formyl, lower alkanoyl, aroyl,cyclohexylcarbonyl, lower alkoxycarbonyl, aryloxycarbonyl, loweralkylsulfonyl, arylsulfonyl, carbamoyl, lower alkylcarbamoyl,arylcarbamoyl, furoyl, et. The alkanoyl and alkylsulfonyl groups can besubstituted as described above in the definition of R. Acetyl,propionyl, butyryl, cyanoacetyl, chloroacetyl, phenylacetyl,methoxyacetyl, methylthioacetyl, methylsulfonylacetyl, methoxycarbonyl,propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl,propylsulfonyl, butylsulfonyl, Z-cyanoethylsulfonyl,Z-methoxyethylsulfonyl, and 2-chloroethylsulfonyl, are examples of thealkanoyl, alkoxycarbonyl, and alkylsulfonyl groups which A canrepresent. The aryl group of the aroyl, aryloxycarbonyl, arylsulfouyl,and arylcarbamoyl group is preferably monocyclic, carbocyclic aryl suchas unsubstituted phenyl and phenyl substituted with, for example, loweralkyl, lower alkoxy, halogen, etc. Toyly, anisyl, p-bromophenyl, ando,p-dichloro-phenylare typical of such aryl groups. Dimethylcarbamoyl,ethylcarbamoyl, propylcarbamoyl, and butylcarbamoyl are illustrativealkylcarbamoyl groups which A can represent.

Examples of the substituents represented by R and R appear hereinabove.

Particularly fast dyeings on polyester materials are obtained from thecompounds having the formula R represents a group having the formula Euin n R" N NO 1 L i l or E -LS I wherein red dyeings having excellentfastness to light and sublimation on polyester fibers and has thestructure:

OzN -N=N N cH, CHa- COOCH: OzN N=N N N NHC oorra l NHCOCH CmQOOCHaproduces bright reddish blue shades on polyester fibers.

EXAMPL E 2 EXAMPLE 5 2,6 Dichloro-4-nitroaniline (2.07 g., .01 m.) isdis- ...zfgtssrsrnif-ts. at zslzainaifiuagfH2504atIOOmtemPemtIeYe-Thf g.of crushed ice, and then a solution of 3.6 g. NaHO in 3 :33: figgi f ggi g i g i g 8 ml. water is added all at once. The diazotization isstirred o at 0-5 C for 1 hr and then the solution is added to a at 2 3 gatlld i' adiled 25 so utlon 0 met y ozenzy anl lno p-to uate g. F agg5511 52 6; g i fl" f g i gg fi g ifig dissolved in 100 ml. of 1:5 acid.The reaction mixture is alcid cgupling' g C :3 i tra'l buffered by theaddition of solid ammonium acetate until a test sample is neutral toCongo Red paper. After allowiizg ggg figfi gg ggg g fi f fi gig g i g ggggg ing to couple 1 hr the mixture is drowrlilerrl1 with water;

in water. The product is collected by filtration, washed 3 332333; i fiiiz g g g aggfi gi z ig fi with water, and air dried. It has thefollowing structure Q N N z N CH COOC QOOCH. 25 51 Q NHCOCH; Thiscompound produces bright scarlet Shades on D b produces bIOWl'llShyellow shades on polyester fabrics. ester fibers. EXAMPLE 6 EXAMP 32-Chloro-4,6-dinitroaniline (2.18 g.) is diazotized and Substitution of2.05 g. of 2-chloro-4-methy1sulfonylcoupled to 2 "j j aniline in Example1 for the amine diazotized in that ex- Y'} Y afllllne COrdmg to theprocedure ample yields the dye 4-(2'-chloro-4'-methylsulfonylphen-Example The i 61110104 ylazo) 3 acetamido N benzyl N (4 methoxycarbonyld1n1trophenylazo-2-methoxy--acetamldo-N-benzyl-N-(4- benzyl) anilinewhich give orange dyeings having methoxycarbonylbenzyl)aniline, producesa navy blue standing resistance to sublimation, on polyester fibers.Shade on Polyester fibers' The azo compounds set forth in Table II, areprepared EXAMPLE 4 according to the porcedures described in Examples 1-62-Cyano-4,6-dinitroaniline (2.07 g., .01 m.) is dissolved and conform tothe general formula in 75 ml. of conc. H 80 at about 0 C. A nitrosylsulfuric 40 acid solution prepared by adding 0.72 g. NaNO to 5 ml. 3 2 Rof conc. H 80 is added portionwise at -5 to 0 C. after being stirred 2min. at about 0 C., the diazonium solution is added to a cold solutionof methyl u-(3-acetamido-N- a i s CHI-Q benzylanilino)-p-toluate (3.88g., .01 m.) dissolved in 4.5 (Yb 6 m1. of 15% H plu 40 ml. of 1:5 acid.After allowing h to stand 15 min. the coupling mixture is drowned with Weremnls water. The product is collected by filtration, washed with Thecolor for each of the compounds appearing in Tables water, and dried inair. The product II through VI refers to dyeings on polyester fibers.

TABLE II Example Position 01 number R-R-R7 (Y)n R R C0OR4 R4 Color 7ate-sass 18sa 1 as s 2:6:di:Cl-4 NO: 3 NHCOCHs -cH H 4 oH Red-biewn. 1O2,6-(1i-C1-4-N0z 3-NHCOOCzH5 -CH2 H 4 CH3 D0.

2,6-di-Cl-4-NO 2,5-di-CH; CH2- H 4 CH; Brown 2-c1-4-N0 3-CH3 CH2- H 4-CH: Red. E-NHCOCH; -0H4CH4- H 4 ---CH; Red. z-ssssss us e a s s- 3NHCOCH: --CH; H 2 CE: Rial 3NHCOCH5 CH2- H 4 -CH; Red. 3-NHCOOC4HI -CHz-H 4 CH; Red. 3-NHSO2C -CH: H 4 CH Red. S-NHSOzCH; -CH4CH4 4-01 4 --CH3Red. 3-NHCONHCaHs -0H4 H 4 -C4H5 Red. B-NHCOCeHi-D-OCH; -0H2-- H 4 -C HRed. 3-NHCOOH2C1 -oH4- H 4 CHzCH(CHs)4 Red. 3-NHCOCH2COH5 -0H.0H,-d-OCH; 4 3H1 Red. 2-Cl-4-N04 3-NHCOCH4CN CH4- H 4 CH; Red. 2-Cl-4-NO:S-NHCOCHrSOHs CHT H 3 -0H, Red. 2-Cl-4-NO: fi-NHCOCHzSOaCH: CH: H 4--CH; Red.

a 2 as :eNHcooiL -OH: H s :OH: i I 3-NHCOCH; CH4 4-0H a -0H, D0. 32fiNHCOGHr 13 iggOCH; i g% Do. 34 a-NHCOCH; A111: H a 4 on: orar igi 35amt-N04 S-NHCOCH; oH2 H 4 CH; Bordeaux. 38... 4-Cl-2-Br-6-NO: 3-NHCOCH;-oH4- H 4 --CH3 Red. 37 -SO2 NHCOCH; -CH:- H 4 -CH; Orange. 38.-2-SO2CHzCHnCHaCH; 3-NHCOCH; CH1- H 4 CH; D0. 99 4-SO4CH; 3-NHCOCH; OH4 H4 CH; D0

TABLE IICntinue'd Position of R -R-R (Y)n R R COOR R C0101 4-S02C8H53-NHCOCH: CHz- H 4 CH: Orange 2-Ol-4 SOzCH: a-NHCOCH: CHz- H 4 CH:Scarlet. 2-C1-4-SO2CH3 3-NHSO2CH: CHz- H 4 CH3 Orange. 2-Cl-4SO2CHz3-NHCOC5H5 CH2- 4-CH: 3 CzHs Scarlet. 2,4-d1-SO2CH: 3-NHCOCH3 CHzCHr- H4 CH3 Red. 2,4-d1-SO2CH: S-NHSOzCaHrp-CH: CHz- H 4 CH: Red.2-SO2CHs-4-NO2 3-CH8 CHz- H 4 CHs Red. 2-SOzCHa-4-NO2 3-NHCOCH: CH2- H 4CH3 Bordeaux.-

48.. 2-SOzCHs4-NO2 3-NHCOCH3 CHz- 4-01 4 CH: D0. 49.. 2-SO CHa-4-NO23-NHCONHC2H5 CH2- H 4 CH: D0. 50..- 2-SOzCHa-4-NO2 3-NHCONH2 CH2' H 4CH: D0. 51-- 2-SOzCHa-4 SCN B-NHCOCHz CH2- H 4 CHa Scarlet. 52.. 4-Cl-2SO2CH: 3-NHCOCHs CH2- 3-OH 4 CH: D0. 53-. 4Br-2-SO2C2H5 S-NHCOCH: CH2- H4 CH: DO. 54.. 4,6-di-Cl-2-SO2CH: 3-NHCOCH: CHz- H 4 CHs D0. 55..2-CN-4-N0z a-NHCOOCH: OHz- H 4 CzHs Red. 56.- 2-COOCzHs-4-NO: S-NHCOCHaCH2- H 4 CH: Red. 2-CFa-4N02 3-NHSO2CH: CH2- H 4 CH: Red. 58 4-CFs-2-NO23-NHCOCH: CHz-- H 4 -CH: Scarlet. 59 2-NO -4-SCN 3-NHCOCHa CHz- H 4 CH:DO. 60 2-NO2-4SO2N(C2H5)2 B-NHCOCHa CHr- H 4 CH: D0. 612-SOzN(C2Hs)2-4-NO2 B-NHCOCHs CHz- H 4 CH: Red. 622-SOzNHCzH5-4,6-dl-NO1 3-NHCOCH3 --CH2- H 4 CH: Blue. 63 2-COOCH-4,6-di-N0z 3-NHCOOC2H5'2-OCH3 CH2- H 4 CHa D0. 64 2-CF84,6-d1-NO23-NHCOCaHs CHr- H 4 CH: D0. 65.. 2COCHs-4,6-d1-NO2 3-NHCOCHa CH2- H 4CH: D0.

2-C1-4,6-dl-N02 3-NHCOCH8 CHz- Cl 4 CH; Violet. 67-. 2-Br-4,6-dl-N0z2-OCHa-5-NHCOCH: CHg- H 4 CzH: Blue. 68.. Z-CI-4fird1-N0z 2-OCzH-5-NHCOCHa --CHz-- H 4 CH: D0. 69.. 2-C1-4,6-di-NO2 2-OCH3-5-NHCOCH:CHz- H 4 CH: D0. 70-. 2-Ol-4,6-di-NO2 Z-OCHa-S-NHCOCH: CH2 H 4 CH: D0.71-.- 2-Cl-4,G-di-NO2 2-OCHa-5-NHCOCH: CH2- H 4 CH: DO. 72.-..2-Cl-4,6-di-NO2 2-OCHr5-NHCOCH3 CH2- H 4 CH: D0. 73.. 2-CN-4,6di-N022-CH3-5-NHCOCH CH2- H 4 CH: D0. 74.- 2-CN-4,6-di-NO2 3-NHCOOC2H5 CH2 H 4CH; Do. 75.- 2CN-4,6di-N0z 3-NHCOC8H4-p-OCH CHg- H 4 CH: DO.2-CN-4fiHli-NO2 3-NHCOCH3 CHz- H 3 CHa D0. 77-. 2-CN-4,6di-NO2 3-NHCOCHsCHz- H 4 CzHs D0. 78 2-CN-4,6-di-NO2 3-NHCOCH3 CHz 4-COOCH3 4 CH; Do. 792-CN-4,6-di-NO2 2-OCH3-5-NHCOCH3 CHr- H 4 CH: Turquoise. 802CN-4,6di-N02 2-0 CHg-fi-NHC 0 CH3 CH2- 3-O CH 4 CH; D0. 812-CN4,6'diNOz 2-OOH3-5-NHCOCH CHz- 4-131 4 CHs D0. 82 2-CN-4,6'di-NO22-OCH -5-NHCOCH3 CHaCHz- H 4 CH: D0. 83-. 2-SO2CHs-4fi-(li-NO: E-NHCOCH:CHz- H 4 CH: Blue. 84-. 2-Cl-6-CN-4-NO 3NHCOCHs CHz- H 4 CH; D0 85...2,4 di-Cl S-NHCOCH: CHr- H 4 CH: Yellow 86.- 4'SOzN(CH3)a S-NHCOCH:--CH2- H 4 GH: Orange. 87-. 40000211: 3-NHCOCH: CHz- H 4 CH; Do 88-.4-CN E-NHCOCH: CHr- H 4 CH; D0. 89-- 2,4-di-CN 3PNHCOCHa CHz- H 4 CH;Red. 90-. 2-Ol-4 COCH: 3-NHCOCH; CHg- H 4 CH; Orange 91.- 2-CHa-4-NO3S-NHCOCH: CH2-- H 4 CH: Scarlet 92-. 4-C0NH2 3-NHCOCsH CHz- H 4 CH;Orange 93-- 4-CON(C2H5)2 3-NHCOCH3 CHr- H 4 CH; 0, 94 2-COCHs-4-NO23-NHSO2CH3 C'Hz- H 4 CH; Red. 95 4-NHCOCH: 3-NHCOCH8 CHz- H 4 CH: YellowEXAMPLE 96 45 colors polyester fibers a reddish blue shade and exhibits2-Chloro-4,6-dinitroaniline (2.18 g.) is diazotized and coupled withN-benzyl-N-(p-methoxycarbonylbenzyl)-1- naphthylamine (2.91 g.)according to the procedure described in Example 1. The product givesviolet dyeings on polyester fibers and has the structure I CH:

1 g cmQ-coocm EXAMPLE 97 To 2.9 g. of 2-amino-5-nitrothiazole, stirredin 25 ml. of water, is added 13.6 ml. of conc. H 50 Solution occursimmediately. The solution is cooled to C. and a solution of 1.4 g. NaNOin 10 ml. conc. H 50 is added below 5 C. Stirring is continued at about5 C. for minutes and then the diazonium solution is added to a coldsolution of 7.74 g. of methyl a-(3-acetamido-N- benzylanilino)-p-toluatein 120 ml. of 1:5 acid, plus 80 ml. of 10% HCl. After allowing to couple15 min. at about 5 C., the mixture is drowned with water. The dye iscollected by filtration, washed with water, and dried in air. Theproduct N l CH:- l Q O2N N=N N CH 000cm NHCOC a excellent sublimationfastness.

EXAMPLE 98 To 5 ml. of cone. H is added 0.72 g. dry NaNO portionwisewith stirring. The solution iscooled and 100 ml. of 1:5 acid is addedbelow 15 C. The mixture is cooled further and 1.43 g. ofZ-amino-S-carbamoylthiazole is added followed by 10 ml. 1:5 acid, all at0-5 C. After diazotizing at 0-5 C. for 2 hr. the solution is added to acool solution of methyl a-(3acetamido-N-benzylanilino)- p-toluate (3.87g.) in 60 ml. of 1:5 acid plus 40 ml. of 10% HCl. The reaction is keptcold and buffered with solid ammonium acetate until a test sample isneutral to Congo Red paper. After allowing to couple 1 hr., the mixtureis drowned with water. The product is collected by filtration, washedwith water, and dried in air. The azo compound obtained produces heavyred shades possessing excellent fastness on polyester fibers. It has thestructure NHC OCH:

The thiazolylazo compounds appearing in the examples of Table HI areprepared by the procedures described in Examples 97 and 98 and conformto the general formula R3 Q 00.. SEQ

It -t 12 solution of 0.84 g. NaNO in 5.0 ml. conc. H 80 is addedportionwise below C. The diazotization is stirred for 2 hr. at about 0C. and then added to a solution of 3.26 g. methyla-(3-acetamido-N-benzylanilino)-p-toluate dissolved in 75 ml. of 15% H80 all below 15 C. The temperature is kept at 0-5 C. for 1 hr. and thencoupling mixture is drowned with water. The product is colo \9 OR 10lected by filtration, washed with water, and an dried. The

TABLE 111 Example Position of number R (Y)u R R -C0ORI 3-011; OH2- H 4a-NHcocH, -cH2cH2- H 4 3-NHCOGH; -0H- 4-CH; 4 3-NHCOCH OCH; -0H, 4-01133 a-NHOHo -0H- 3-COOCH; a 3-NHCOCH1CN -CH2-- H 4 ii-NHCQCHzCgH -CHz H 43-NHCOC5H5 --CH2-- H 2 3-NHCONHCaH CH2- H 4 S-NHCONHCQH; -CH:- H 43-NHCOOC2H5 -oH- H 4 2-CHs-5-NHCO CH3 CH2- H 4 2-OCH3-5-NHCOCH: cH2- H 42-OCHa-5-NHCOC H5 CH2- H 3 3-NHCOC0H11 -CH2 H 4 3-NHCO0CzH -CH2CH2- 4-0H4 3-NHCOCH; H2- H 4 3-NHCOCH, CHz- 4000013; 4 a-NHCOCHz -CH2 H 43-NHSO2CH: CH2 H 4 a-NHoocH, CH:|- H 4 a-NHSOzCcHrD-Cl -OH2- H 43-NHCOCH; -CH-.- H 4 3FNHCOCH3 -CHz- H 4 B-NHCOOH; -CH: H 4 s-NHCOCH,-CH,- H 4 2 3-NHCOC4H -n -oH2- H 4 6 4-CH3-5-NO2 3-NHCOCH2OCH5 -CH- H 4127..- 4-CH3-5-NO: 3NHSO2OH3 -0H,- H 4 128 fr-CHs-S-NO: 3-NHSO2C4H5 CH2-H 4 -CH3 D EXAMPLE 129 azo compound obtained gives fast red dyeings onpoly- Sodium nitrite (0.76 g.) is added portionwise to 5 ml. of cone. H80 This solution is cooled in an ice bath and 10 ml. 1:5 acid is added,keeping the temperature below C. This mixture is stirred at 0-5 C. and1.75 g. of Z-amino-6-cyanobenzothiazole is added, followed by 10 ml. of1:5 acid. The diazotization is stirred at 0-5 C. for 2 hr. and is thenadded to a solution of 3.26 g. methyla-(3-acetamido-N-benzylanilino)-p-toluate in 100 ml. of 1:5 acid. Thecoupling is butfered with solid ammonium acetate and allowed to react atabout 5 C. for 2 hr. After drowning in water, the product is collectedby filtration, washed with water, and dried in air. The product producesbright fast red shades on polyester fibers and has the structure esterfibers and has the structure:

C NHCOCH;

The azo compounds of Table IV are prepared by the procedures describedin Examples 129 and 130 and conform to the general formula l N o N=N -NN s Q Q m I CH -coooH, NHooon. r- S EXAMPLE 130 (Y). Q? To 2.28 g. ofZ-amino-6-methylsulfonylbenzothiazole suspended in 24 ml. is added 26.2g. cone. H After all the amine has dissolved, the solution is cooled anda TABLE IV Position (Y)'n R R 04-00011 R4 Color CH: H 4 CHa Red. 3-CH;-oH,- H 4 -CH; Red. 3-Cl CHr- H 4 -CH: Red. 2-CH3 'CH:- H 4 -CH3 Red.3-NHCOCHs CH2CH2 H 4 CH: Red. Z-OCHa-iZ-NHCOCH: -CH:- H 4 -CH3 Violet;s-NnoootHt CH2- H 4 -orn Red, 3-NHSO2CHa cH4- 40H, 3 -o,H, Red.3-NHS02CH3 -CH= H 2 CH; Red. 3-NHCONHCgH; CH;- H 4 CH; Red aNHooom -CH:H 4 -0H, Red. H ---CH7 H 4 CH; Bordeaux; 3-011, -CHz- H 4 CH; Do.3-NHCOCH; -CH-.- 40H; 4 -CH3 Violet.

TABLE IV-Continued Example Position number R (Y)n R R ot-COOR R Color145 fi-NO: 2-CHs-5NHCOCH: -CHr- 4-CH: 4 -CH: Do. 146. G-NQ: 2-OCH-NHCOC3H5 CH| 4-CH 4 -CH; Blue. 147- 4,6-d1-NO; 3-NHCOCH; --CH:- H 4-CH1 Do. 148 4-Br-6-SOzCH; 3-NHCOCH; -CH:- H 4 -CH; Violet. 149. 1-013-NHCOCH: CH:- H 4 -CH: Red. 150 4,6-di-C1 3-NHCOCHs CHr- H 4 -CH Red.151... fi-Br 3-NHCOCH| --CH|- H 4 -CH| Red. 152 G-SOzNH: 3-NHCOCH: CH| H4 -CH: Red. 6-SO1N(CH;) S-NHCOCH; CH;' H 4 -CH; Red. G-COOCaH;fi-NHCOCH: -CHr- H 4 -OH| Red. S-COCH 3-NHCOCH; -CH1 H 4 CH1 Red.G-NHCOCH: 3-NHCOCH| CHg- H 4 CH: Bed. G-SCH; 3-NHCOCH: CH:- H 4 -CHIRed. 158. 6SCH; 3-NHCOCHa CH| H 4 -CH; Red. 159... G-CHl! S-NHCOCH; CHr-H 4 CH; Red. 160 G-SOQCHICHICN 3-NHCOCHI -CH:- H 4 -CH| Pink.

EXAMPLE 161 ml. of 10% HCl. The coupling is kept cold and is buf- Sodiumnitrite (0.72 g.) is added to 5 ml. of conc. 2

H 50 with stirring. The solution is cooled and 10 ml. of 1:5 acid isadded below 15 C. The mixture is cooled fur= ther andZ-amino-S-ethylthio-l,3,4thiadiazole (1.61 g.) is added at -5 0.,followed by an additional 10 m1. of 1:5 acid. After stirring at 0-5 C.for 2 hr., the diazonium solution is added to a cooled solution ofmethyl a-(3-acetamido-Nbenzylanilino)-p-toluate (3.87 g.) in 60 ml. of1:5 acid, plus 40 ml. of 10% HCl. The reaction mixture is buffered withammonium acetate until a test sample is neutral to Congo Red paper. Thecoupling mixture is allowed to stand for 1 hr. and then water is addedto precipitate the dye. The product is collected by filtration, washedwith water, and dried in air. The product, which has the structureproduces brilliant scarlet shades on polyester fiber and possessesexcellent fastness properties.

EXAMPLE 162 To 1.63 g. 2-amino-5-methylsulfonyl-1,3,4-thiadiazoleslurried in 24 ml. water, is added 14 ml. conc. H 80 The resultingsolution is cooled to 0 C. and a solution of 1.44 g. NaNO in 10 m1.conc. H 80 is added below C. The diazotization is stirred at ice-bathtemperature for 2 hr. It is then added to a cold solution of 4.4 g.3-benzamido-N,N-di(3 methoxycarbonylbenzyl)aniline in 100 ml. of 1:5acid. The coupling is buffered with solid ammonium acetate and allowedto stand 2 hr. It is then drowned in water. The dye is collected byfiltration, washed with water, and air dried. The azo compound obtaineddyes polyester fibers bright red shades having excellent fastnessproperties and has the formula Sodium nitrite (0.72 g.) is added to 5ml. conc. H 80 The solution is cooled and ml. of 1:5 acid is added belowC. After cooling further, S-amino-3-methylthio-1,2,4-thiadiazole isadded below 5 C., followed by an additional 10 ml. of 1:5 acid at thesame temperature. The diazotization reaction is stirred at 0-5 C. for 2hrs. and then the diazonium solution is added to a cold solution ofmethyl a-(3-acetamido-N-benzylanilino)-p-toluate (3.87 g., .01 m.)dissolved in 60 ml. of 1:5 acid, plus 40 fered by the addition ofammonium acetate until a test sample is neutral to Congo Red paper. Thecoupling is allowed to stand 1 hr. and is then drowned with water. Theproduct is collected by filtration, washed with water and dried in air.The dye r S Q I CHa- C 0 Gem NH O O C produces beautiful red shades onpolyester fibers and has excellent lightfastness and resistance tosublimation.

The thiadiazolylazo compounds set forth in the examples of Table V areprepared by the procedures described in Examples 116 through 163 bydiazotizing the appropriate 2-aminothiadiazole and coupling theresulting diazonium salt with an alkyl a-N-benzylanilinotoluate. Thecompounds of Table V conform to the general formula Cm-Q-Q o 00H.

m which diazo component R 1s a group having the structure NN R"|N R L J(1, z, 4 or N J'- 1, 2, 4

TABLE V Example number R R" dlazo isomer (Y)u Color CHIS-1,3,4 H Orange.165. CHIS-1,3,4 3-CHI D0. 166. OILS-1,3,4 S-NHCOCaHl Scarlet 167-CHrS-1,3,4 3-NHCOC6HI D0. 168 CgH;S-1,3,4 3NHCONHI D0. 169 n-CiHaS-1,3,43-NHCOCH: D0. 170....... n-C4H S-1,3,4 3-NHSO1CH: D0. 171- CsHnS-1,3,43-NHCOCH: D0 172- CHzSOz-LBA Z-NHOOOCnHI Violet. 173- CH;SO2-1,3,43-NHCOCsHg D0. 174- CuH -1,3, 3-NHCOCHI Orange 175. OIL-1,3,4 3-NHSO2CHIDO. 176.-. p-Cl-CoHi-lfiyi 3-NHCOCH: Red. 177 p-CHa-CaH4- A 3-NHCOCH:Red. 178.-....- p-CHaO-CcHa-LBA 3-NHCOCHI Red. 9 Cl-1,3,4 3-NHCOCH| Red.Br-1,3,4 3-NHCOCHI Red. CuH CHaS-1,3,4 3-NHCOCH: Red. CHE-1,2,43-NHCOOC1H Red. Chins-1,2,4 Z-NHSOaCaHi Red. OHS-1,2,4 3-NHCONHClHI Red.C:H S-1,2,4 B-NHCOCzH Red. 186 CHrSOa-LZA 8-NHCOCH: Violet. 187.-.. CaSOz-1,2,4 2-OCHr5-NHCOCHI Do. 188- H:S03-1,2,4 2-CHi-5NHCOCHI D0. 189--C H CH1S-1,2,4 3-NHCOCHl ed. 190.. (CHa)aCHCH1S-1,2,4 B-NHCOCH: Red.

EXAMPLE 191 To 5 ml. of concentrated sulfuric acid is added portionwise0.72 g. of sodium nitrite with stirring. The nitrosoyl sulfuric acidsolution is cooled and 10 ml. of

15 1:5 acid (1 part propionic to 5 parts acetic) is added below 10 C.2-amino-3-nitro-5-isobutyrylthiophene is added to acid solution followedby 10 ml. of 1:5 acid, all at 05 C. The mixture is stirred at -5" C. forone hour. The diazonium solution is added to a cold solution of methyla-(3-acetamido N beniylanilino)-p-toluate (3.87 g.) in 60 ml. of 1:5acid plus 40 ml. of HCl. The coupling mixture is stirred occasionallyfor 1 hr. and is then drowned with water. The blue dye is collected byfiltration, washed with water, and dried in air. The dye 10 0 TIT-N02tcrmlcnii S Jams-- NHC OCH;

ca go 0 00m The compounds conform to the formula The compounds of theinvention can also be applied to polyester textile materials by the heatfixation technique described in US. Patent 2,663,612 and in the AmericanDyestuff Reporter, 42, 1 1953). The following procedure describes howthe azo compounds of the invention can be applied to polyester materialsby the heat fixation technique.

EXAMPLE 211 A mixture of 500 mg. of the compound of Example 4, 150 mg.of a sodium lignosulfonate dispersing agent (Marasperse N), 150 mg. of apartially desulfonated sodium lignosulfonate (Marasperse CB), 0.5 ml.glycerin, and 1.0 ml. of water is ground in a microsize container (anaccessory for a l-quart size Szegvari Attritor) for approximately 3.5hours. Enough /s-inch stainless steel balls are added to provide maximumgrinding. When the grinding is complete, the entire contents are pouredinto a beaker and 100 ml. of water are used to wash the remaining dyepaste from the micro-container. The dye paste is then heated slowly to65 C. with continuous stirring.

A thickener and penetrating mixture is prepared by mixing:

1 m1. of a complex diary] sulfonate surfactant (compound 8-8),

3 ml. of a 3% solution of a sodium N-methyl-N-oleoyltaurate (IgeponT-Sl),

8 ml. of a 25% solution of natural gums (Superclear SON), and sufiicientwater to bring the volume to 100 ml. The thickener and penetratingmixture is added to the b dye paste, the volume is ad usted to 200 ml.and the TABLE VI (Y)n R Color 3-NHCOCH: H Blue. 3-NHCOCuHl H Do.3-NHCOC:H 4-CH3 D0. 3-NHSO1CH1 H D0. (CHghOHCO-S-NO: 3-NHCOCH; 4-Br D0.197-- 5-(CH;)2CHCO-3NO1 3-NHCHO H DO. 198-- 5-(CHa)zCHCO-3-NO1 3NHCOCIHnH D0. 199-- 5-(CH3)2CHCO-3-NO2 3-NHCOC Hs H Do. 200-- 5-(CHa)aCHCO-3-NO3-NHCONHC2H| H D0, 201-. 5-(CHa)2CHCO-3-NO: 2-OCH;-5-NHCOCH H Blue-green202.. 5-(CHz)2CHC0-3-NO2 3-NHCOC:H4.C1 H e. 203.. 5-p-NO2-C H4CO3 NO]3-NHCOCH; H D0. 204-- 5-1J-C1-05H4CO-3-N05 3-NHCOCH: H D0. 205-.5-CH3CHaCHz-3-NO; 3-NHSO1C1H4C1 H Do. 206.. 5-di-N z 3-NHCOCH: HBlue-green; 207.. 3,5-di-S02CHI 3-NHCOCH(CH;) H Turquoise. 208.. 3-NO23-NHCOC4Hn-n H lue. 209 5-COOCzH a-NHCOCH: H D0.

The compounds of the invention can be used for dyeing linear polyestertextile materials in the manner described in U.S. Patents 2,880,050;2,757,064; 2,782,187; and 3,043,827. The novel monazo compounds arewater-insoluble, i.e. substantially water-insoluble, and therefore theycan be applied to polyester fibers according to conventional dispersedyeing techniques. The following examples illustrates a carrier dyeingprocedure for applying the azo compounds of the invention to dyepolyester textile materials.

EXAMPLE 210 The azo compound (0.1 g.) is dissolved in 10 cc. of2-methoxyethanol. A small amount (3-5 cc.) of a 3% sodium ligninsulfonate aqueous solution is added, with stirring, and then the volumeof the bath is brought to 300 cc. with water. Three cc. of anionicsolvent carrier (Tanavol) is added to the bath and 10 grams of a textilefabric made of poly(ethylene terephthalate) fibers is placed in the bathand worked 10 minutes without heat. The dyeing is carried out at theboil for one hour. The dyed fabric is removed from the dyebath andscoured for 20 minutes at 80 C. in a solution containing 1 g./l. neutralsoap and 1 g./l. sodium carbonate. The fabric is then rinsed, dried inan oven at 250 F. and heat set (for the removal of residual carrier) for5 minutes at 350 C.

mixture is agitated for 15 minutes. The dye mixture is then filteredthrough folded cheesecloth to remove the stainless steel balls and itthen is added to the reservoir of a Butterworth padder where it isheated to about 45- 60 C.

10 g. of a fabric of poly(ethylene terephthalate) fibers and 10 g. of afabric of 65/35 spun poly(ethylene terephthalate)-cotton fibers are sewntogether, end-to-end, and padded for 5 minutes of continuous cyclingthrough the dye mixture and between three rubber squeeze rollers of thepadder. Dye mixture pick-up is about 60% based on the weight of thefabrics.

The padded fabrics are then dried at 200 F. and then heat-fixed for 2minutes at 415 F. in a forced air oven. The dyed fabrics are scoured for20 minutes at 65-70 C. in a solution containing 0.2% sodiumhydrosulfite, 0.2% sodium carbonate and 1.7% of a 3% solution of sodiumN-methyl-N-oleoyltaurate and then dried. The dyed fabrics possessexcellent brightness and exhibit outstanding fastness to light andsublimation when tested according to the procedures described in the1966 edition of the Technical Manual of the American Association ofTextile Chemists and Colorists.

The heat fixation dyeing procedure described above can be varied by thesubstitution of other dispersing agents, surfactants, suspending agents,thickeners, etc.

17- The temperature and time of the heat-fixation step can also bevaried.

Polymeric linear polyester materials of the terephthalate sold under thetrademarks Kodel, Dacron and Terylene are illustrative of the lineararomatic polyester textile materials that can be dyed with the compoundsof our invention. Examples of linear polyester textile materials thatcan be dyed with the compounds of the invention are those prepared fromethylene glycol and dimethylterephthalate or from cyclohexanedimethanoland dimethylterephthalate. Polyesters prepared fromcyclohexanedimethanol and dimethylterephthalate are more particularlydescribed in US. Pat. 2,901,446. Poly- (ethylene terephthalate)polyester fibers are described, for example, in US. Pat. 2,465,319. Thepolymeric linear polyester materials disclosed in US. Pats. 2,945,010,2,957,745, and 2,989,363, for example, can be dyed. The linear aromaticpolyester materials specifically named have a melting point of at least200 C. The poly(ethylene terephtblate) fibers which are dyed with thecompounds of the invention are manufactured from amelt of a polymerhaving an inherent viscosity of at least 0.35 and preferably, about 0.6.The inherent viscosity of the poly- (1,4cyclohexylenedimethyleneterephthalate) polymer is also at least 0.35. These inherent viscositiesare measured at 25 C. using 0.25 g. polymer per 100 ml. of a solventconsisting of 60% phenol and 40% tetrachloroethane. The polyesterfabrics, yarns, fibers and filaments that are dyed with the novel azocompounds can also contain minor amounts of other additives such asbrighteners, pigments, delusterans, inhibitors, stabilizers, etc.Although the compounds of the invention are particularly suitable fordyeing polyester textile materials, the compounds can also be used todye other synthetic, hydrophobic textile materials such as celluloseacetate, modified polypropylene, polyamide, modacrylic, etc. fibers.

The invention has been described in considerable detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be effected within the spirit andscope of the invention as described hereinabove.

We claim:

1. A compound having the formula wherein R is a group having the formulawherein R is lower alkyl, lower alkoxy, nitro, chlorine, bromine, loweralkylsulfonyl, carbamoyl, lower alkylcarbamoyl, di-lower alkylcarbamoyl,lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl, di-loweralkylsulfamoyl, cyano, thiocyanato, trifiuoromethyl, phenyl, loweralkylphenyl, lower alkoxyphenyl, or chlorophenyl;

R is nitro, chlorine, bromine, lower alkylsulfonyl, loweralkoxycarbonyl, sulfamoyl, di-lower alkylsulfamoyl, cyano, thiocyano, orlower alkylthio;

R is lower alkyl, chlorine, bromine, lower alkylthio, benzylthio,cyclohexylthio, or lower alkylsulfonyl;

R is lower alkylthio, cyclohexylthio, benzylthio, or loweralkylsulfonyl; and

R is lower alkanoyl, benzoyl, lower alkylbenzoyl, lower alkoxybenzoyl,or nitrobenzoyl;

R is p-phenylene; p-phenylene substituted with lower alkyl, loweralkoxy, halogen or the group NHA in which A is formyl, lower alkanoyl,lower cyanoalkanoyl, lower alkoxyalkanoyl, lower alkylsulfonylalkanoyl,lower phenylalkanoyl, benzoyl, lower alkoxybenzoyl, cyclohexyl carbonyl,lower alkoxycarbonyl, lower alkylsulfonyl, arbamoyl, loweralkylcarbamoyl, or phenylcarbamoyl;

R is alkylene from 1 to about 2 carbon atoms;

R is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, hydroxy, orlower alkoxycarbonyl; and

R is lower alkyl. 2. A compound according to claim 1 having the formula4. A compound according to claim 1 having the formula 1 F'Q B S N=N N ocar-Gil 0 n4 wherein R is cyano, nitro, lower alkylsulfonyl, loweralkoxycarbonyl, or thiocyanato; A is lower alkanoyl, benzoyl, loweralkoxycarbonyl, lower alkylsulfonyl, or alkylcarbamoyl; R is hydrogenlower alkyl, lower alkoxy or chlorine and R is lower alkyl.

5. A compound according to claim 1 having the formula NHC OC I IHA R islower alkyl, lower alkylthio, cyclohexylthio, phenylthio, loweralkylsulfonyl, or lower alkoxycarbonyl;

A is lower alkanoyl, benzoyl, lower alkylsulfonyl, lower alkoxycarbonyl,or lower alkylcarbamoyl;

R is hydrogen, lower alkyl, lower alkoxy, or chlorine and R is loweralkyl,

6. Acompound according to claimlhaving the formula R is hydrogen, loweralkyl, lower alkoxy, or chlorine N-N and I I GHQ R is lower alkyl. 01mgo 10. A compound according to claim 1 having the fors Q a 5 mula 0H,OCH; NHC 0cm 0 N0:

7. A compound according to claim 1 having the formula El 1 L Q o 1NHoocH.

S \zm-Q-Jiom CHr-Q NHA wherein R is lower alkylthio or loweralkylsulfonyl; 15 C 0 0H:

A g fi s ggi gi gg fii figig i gfig lower 11. A compound according toclaim 1 having the for- R is hydrogen, lower alkyl, lower alkoxy, orchlorine and mula R is lower alkyl. N0: CH 8. A compound according toclaim 1 having the formula I S 1 N HO OCH;

| GHQ-C 0 OCH; References Cited NHCOCH;

9. A compound according to claim 1 having the formula UNITED STATESPATENTS 2,864,812 12/1958 Bossard et al 260-146 R I Q 2,871,231 1/1959Stl'aley et al 260-146 R 0 3,483,180 12/1969 Ramanathan 260158 s u3,573,273 3/1971 Seedfclder et al 260l58 IIqHA Q- 3,639,385 2/1972'Weaver et al 260-158 Whereln FLOYD D. HIGEL, Primary Examiner R islower alkanoyl, benzoyl, lower alkylbenzoyl, lower alkoxybenzoyl,halobenzoyl,or nitrobenzoyl; U.S. C1. X.R.

A is lower alkanoyl, benzoyl, lower alkoxycarbonyl, lower alkylsulfonyl,or lower alkylcarbamoyl; 8-41 260-158 471 R

